JP2010095688A5

JP2010095688A5 -

Info

Publication number: JP2010095688A5
Application number: JP2008270161A
Authority: JP
Filing date: 2008-10-20
Publication date: 2011-11-24
Anticipated expiration: 2028-10-20

Description

このように、例４の金属ナノ粒子−導電性高分子複合体を例１８の積層型熱電素子に用いると、出力電流が約１．６倍（＝３．３μＡ／２．１μＡ）になることが予測できる。本発明の実施態様の一部を以下に列記する。
［１］
導電性高分子、及び
保護剤で被覆された金属ナノ粒子を含む、導電性高分子複合体であって、
前記保護剤が、前記導電性高分子の骨格構造の少なくとも一部分及び前記金属ナノ粒子と相互作用する部分を分子内に有する化合物である、導電性高分子複合体。
［２］
前記導電性高分子が、ポリアニリン、ポリチオフェン、ポリピロール、ポリフェニレンビニレン、ポリチエニレンビニレン、及びこれらの誘導体からなる群から選択される、［１］に記載の導電性高分子複合体。
［３］
前記保護剤が、前記導電性高分子がポリアニリンを含む場合、４−アミノチオフェノール、２−アミノチオフェノール、３−アミノチオフェノール、２−アミノベンゼンスルホン酸、２−アミノ安息香酸、３−アミノ安息香酸、４−アミノ安息香酸、２−アミノベンゾニトリル、３−アミノベンゾニトリル、４−アミノベンゾニトリル、２−アミノベンジルシアニド、３−アミノベンジルシアニド、４−アミノベンジルシアニド、Ｎ−フェニル−１，２−フェニレンジアミン、又はＮ−フェニル−１，４−フェニレンジアミンか、あるいはＮ−ビニルピロリドンとＮ−フェニル−Ｎ’−（３−メタクリロイルオキシ−２−ヒドロキシプロピル）−ｐ−フェニレンジアミンとの共重合体から選択され；前記導電性高分子がポリチオフェン又はポリチエニレンビニレンを含む場合、３−（２−チエニル）−ＤＬ−アラニン、４−（２−チエニル）酪酸、２−（２−チエニル）エタノール、２−（３−チエニル）エタノール、２−チオフェン酢酸、３−チオフェン酢酸、２−チオフェンアセトニトリル、２−チオフェンカルボニトリル、２−チオフェンカルボキサミド、２−チオフェンカルボン酸、３−チオフェンカルボン酸、２−チオフェンカルボン酸ヒドラジド、２，５−チオフェンジカルボン酸、２−チオフェンエチルアミン、２−チオフェングリオキシル酸、２−チオフェンマロン酸、２−チオフェンメタノール、又は３−チオフェンメタノールから選択され；前記導電性高分子がポリピロールを含む場合、ピロール−２−カルボン酸、又は１−（２−シアノエチル）ピロールから選択され；前記導電性高分子がポリフェニレンビニレンを含む場合、安息香酸、ベンゼンチオール、ベンゼンスルホン酸、３−ビニル安息香酸、又は４−ビニル安息香酸から選択される、［２］に記載の導電性高分子複合体。
［４］
前記金属ナノ粒子が、金、白金、パラジウム、銀、ロジウム、ニッケル、銅、及びスズ、並びにそれらの合金からなる群から選択される材料で作られる、［１］〜［３］のいずれか１つに記載の導電性高分子複合体。
［５］
前記保護剤のモル数が、前記金属ナノ粒子１モルあたり０．１〜５０である、［１］〜［４］のいずれか１つに記載の導電性高分子複合体。
［６］
前記金属ナノ粒子の含有量が、前記導電性高分子の質量を基準として、０．０１質量％以上である、［１］〜［５］のいずれか１つに記載の導電性高分子複合体。
［７］
（ａ）耐熱性を有する基材と、
（ｂ）薄膜形状で前記基材上に配設されている、導電性高分子を含む少なくとも１つの第１の熱電材料と、
（ｃ）薄膜形状又はワイヤ形状で前記基材上に前記第１の熱電材料から間隔を空けて隣り合わせに配設されて、その隣り合う第１の熱電材料と一緒に単位熱電対を構成する、ｎ型半導体又は金属を含む少なくとも１つの第２の熱電材料と、
（ｄ）前記第１の熱電材料と前記第２の熱電材料が交互して電気的に直列に接続されかつ両末端が開放された回路を形成するように、前記第１の熱電材料の端部と前記第２の熱電材料の端部とを電気的に接続する導電性材料と
を備える、熱電素子。
［８］
前記導電性高分子がポリアニリンである、［７］に記載の熱電素子。
［９］
前記第１の熱電材料が、保護剤で被覆された金属ナノ粒子をさらに含み、前記保護剤が、前記導電性高分子の骨格構造の少なくとも一部分及び前記金属ナノ粒子と相互作用する部分を分子内に有する化合物である、［７］又は［８］のいずれかに記載の熱電素子。
［１０］
前記基材が可撓性である、［７］〜［９］のいずれか１つに記載の熱電素子。 Thus, when the metal nanoparticle-conductive polymer composite of Example 4 is used for the laminated thermoelectric element of Example 18, the output current is about 1.6 times (= 3.3 μA / 2.1 μA). Can be predicted. Some of the embodiments of the present invention are listed below.
[1]
Conductive polymers, and
A conductive polymer composite comprising metal nanoparticles coated with a protective agent,
A conductive polymer composite, wherein the protective agent is a compound having in its molecule at least a part of the skeleton structure of the conductive polymer and a part that interacts with the metal nanoparticles.
[2]
The conductive polymer composite according to [1], wherein the conductive polymer is selected from the group consisting of polyaniline, polythiophene, polypyrrole, polyphenylene vinylene, polythienylene vinylene, and derivatives thereof.
[3]
In the case where the protective agent is such that the conductive polymer contains polyaniline, 4-aminothiophenol, 2-aminothiophenol, 3-aminothiophenol, 2-aminobenzenesulfonic acid, 2-aminobenzoic acid, 3-amino Benzoic acid, 4-aminobenzoic acid, 2-aminobenzonitrile, 3-aminobenzonitrile, 4-aminobenzonitrile, 2-aminobenzyl cyanide, 3-aminobenzyl cyanide, 4-aminobenzyl cyanide, N- Phenyl-1,2-phenylenediamine, N-phenyl-1,4-phenylenediamine, or N-vinylpyrrolidone and N-phenyl-N ′-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylene Selected from copolymers with diamines; the conductive polymer is polythiophene or polythiophene When thienylene vinylene is included, 3- (2-thienyl) -DL-alanine, 4- (2-thienyl) butyric acid, 2- (2-thienyl) ethanol, 2- (3-thienyl) ethanol, 2-thiopheneacetic acid 3-thiopheneacetic acid, 2-thiopheneacetonitrile, 2-thiophenecarbonitrile, 2-thiophenecarboxamide, 2-thiophenecarboxylic acid, 3-thiophenecarboxylic acid, 2-thiophenecarboxylic acid hydrazide, 2,5-thiophenedicarboxylic acid, 2 -Selected from thiophenethylamine, 2-thiophene glyoxylic acid, 2-thiophenmalonic acid, 2-thiophenmethanol, or 3-thiophenmethanol; when the conductive polymer comprises polypyrrole, pyrrole-2-carboxylic acid, or 1 -From (2-cyanoethyl) pyrrole The conductive polymer according to [2], wherein when the conductive polymer comprises polyphenylene vinylene, it is selected from benzoic acid, benzenethiol, benzenesulfonic acid, 3-vinylbenzoic acid, or 4-vinylbenzoic acid. Polymer composite.
[4]
Any one of [1] to [3], wherein the metal nanoparticles are made of a material selected from the group consisting of gold, platinum, palladium, silver, rhodium, nickel, copper, and tin, and alloys thereof. The conductive polymer composite described in 1.
[5]
The conductive polymer composite according to any one of [1] to [4], wherein the number of moles of the protective agent is 0.1 to 50 per mole of the metal nanoparticles.
[6]
The conductive polymer composite according to any one of [1] to [5], wherein the content of the metal nanoparticles is 0.01% by mass or more based on the mass of the conductive polymer. .
[7]
(A) a base material having heat resistance;
(B) at least one first thermoelectric material including a conductive polymer disposed in the form of a thin film on the substrate;
(C) A thin film shape or a wire shape is disposed on the substrate adjacent to each other with a space from the first thermoelectric material, and constitutes a unit thermocouple together with the adjacent first thermoelectric material. at least one second thermoelectric material comprising an n-type semiconductor or metal;
(D) an end portion of the first thermoelectric material so as to form a circuit in which the first thermoelectric material and the second thermoelectric material are alternately electrically connected in series and open at both ends; And a conductive material that electrically connects the end of the second thermoelectric material;
A thermoelectric device.
[8]
The thermoelectric element according to [7], wherein the conductive polymer is polyaniline.
[9]
The first thermoelectric material further includes metal nanoparticles coated with a protective agent, and the protective agent contains at least a part of the skeleton structure of the conductive polymer and a part that interacts with the metal nanoparticles in a molecule. The thermoelectric element according to any one of [7] or [8], which is a compound having
[10]
The thermoelectric element according to any one of [7] to [9], wherein the base material is flexible.

Claims

Conductive polymer, and at least one metal nanoparticles coated with a protective agent, a conductive double coupling material,
The protective agent, the first portion and the compounds which have a second portion that interacts with at least one metal nanoparticle, a conductive double if material having at least a portion of the skeletal structure of the conductive polymer .

(A) a base material having heat resistance;
(B) A first thermoelectric material including a conductive composite material disposed on the substrate in a thin film shape, wherein the conductive composite material is coated with a conductive polymer and a protective agent. At least one metal nanoparticle, and the protective agent has a first part having at least a part of the skeleton structure of the conductive polymer and a second part interacting with the at least one metal nanoparticle. A first thermoelectric material that is a compound;
(C) A thin film shape or a wire shape is disposed on the base material adjacent to each other at a distance from the first thermoelectric material, and constitutes a unit thermocouple together with the adjacent first thermoelectric material. a second thermoelectric material comprising an n-type semiconductor or metal;
(D) electrically connecting an end portion of the first thermoelectric material and an end portion of the second thermoelectric material, whereby the first thermoelectric material and the second thermoelectric material are alternately electrically connected; Electrically conductive materials that form a circuit that is connected in series and open at both ends, and
A thermoelectric device.

(A) a base material having heat resistance;
(B) and are disposed on the substrate with a thin film shape, a conductive polymer including a first thermoelectric material,
(C) A thin film shape or a wire shape is disposed on the substrate adjacent to each other with a space from the first thermoelectric material, and constitutes a unit thermocouple together with the adjacent first thermoelectric material. and including a second thermoelectric material n-type semiconductor or a metal,
(D) electrically connecting an end portion of the first thermoelectric material and an end portion of the second thermoelectric material, whereby the first thermoelectric material and the second thermoelectric material are alternately electrically connected; to that form a circuit connected in series and both ends are opened, and a conductive material, the thermoelectric element.